Actinic ray-sensitive or radiation-sensitive resin composition, resist film, and pattern-forming method using the same

ABSTRACT

Provided is an actinic ray-sensitive or radiation-sensitive resin composition, a resist film formed with the composition, and a pattern-forming method using the same. The actinic ray-sensitive or radiation-sensitive resin composition includes (P) a resin that contains the following repeating units (A), (B) and (C); and a solvent having a boiling temperature of 150° C. or less,
         (A) a repeating unit containing a group capable of decomposing and forming an acid upon irradiation with an actinic ray or radiation,   (B) a repeating unit containing a group capable of decomposing and forming a carboxylic acid by the action of an acid, and   (C) a repeating unit containing a carbon-carbon unsaturated bond.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an actinic ray-sensitive orradiation-sensitive resin composition preferably used insuper-micro-lithography process such as the manufacture of super LSI andhigh capacity microchips and other photo-fabrication processes, a resistfilm formed with the composition, and a pattern-forming method using thesame. More specifically the invention relates to a positive resistcomposition for electron beam, X-ray or EUV ray, a pattern-formingmethod using the same, and a resin for use in a positive resistcomposition.

2. Description of the Related Art

In manufacturing process of semiconductor devices such as IC and LSI,fine process by lithography with a photoresist composition has beenconventionally carried out. In recent years, ultrafine pattern formationof a sub-micron region and a quarter micron region has been requiredwith higher integration of integrated circuits. In such a circumstance,exposure wavelength also shows a tendency to become shorter such as froma g line to an i line, and further to a KrF excimer laser ray. Further,besides a KrF excimer laser ray, development of lithography using anelectron beam, an X-ray or an EUV ray is also now progressing.

In particular, electron beam lithography is positioned as apattern-forming technique of the next generation or the next of the nextgeneration, and positive resist of high sensitivity and high resolutionis desired. For shortening the processing time of wafers, increase ofsensitivity is a particularly important problem. However, pursuit ofhigher sensitization in positive resist for electron beams isaccompanied by not only lowering of resolution but also deterioration ofline edge roughness, accordingly development of a resist satisfyingthese characteristics at the same time is strongly desired. Here, lineedge roughness means that, since the edge at the interface between thepattern of a resist and a substrate irregularly fluctuates in theperpendicular direction to the line direction attributably to thecharacteristics of the resist, the edge is seen unevenly when thepattern is viewed just above. This unevenness is transferred in theetching process of using the resist as a mask and deteriorates electriccharacteristics to lower the yield. In particular, in a super fineregion of 0.25 μm or less, line edge roughness is an extremely importantproblem to be improved. High sensitivity, high resolution, good patternform and good line edge roughness are in a relationship of tradeoff, andit is very important how to satisfy these characteristics at the sametime.

It is also an important problem to satisfy high sensitivity, highresolution, good pattern form and good line edge roughness at the sametime in lithography using X-rays and EUV rays, and solution isnecessary.

As one way of solving these problems, use of a resin having a photo-acidgenerator in the main chain or side chain of a polymer is examined(JP-A-9-325497 (The term “JP-A” as used herein refers to an “unexaminedpublished Japanese patent application”.), JP-A-10-221852,JP-A-2006-178317, JP-A-2007-197718, WO 2006/121096, US 2006/121390, US2007/117043, JP-A-2008-133448 and Proc. of SPIE, Vol. 6923, 692312,2008). However, in the examination of JP-A-9-325497, since thecomposition is a mixed system of a resin having a photo-acid generatorand a dissolution-inhibiting compound capable of increasing solubilityin an alkali developer by decomposition due to an acid, it is difficultto obtain good pattern form and line edge roughness attributable to aheterogeneous mixing property of these materials.

On the other hand, in JP-A-10-221852, JP-A-2006-178317,JP-A-2007-197718, WO 2006/121096 and US 2006/121390, resins having aphoto-acid generating group and a group capable of decomposing by theaction of an acid and increasing the solubility in an alkali developerin the same molecule are disclosed, but it cannot be said that thesensitivity to electron beams, X-rays or EUV rays is sufficient.

Further, a terpolymer comprising hydroxystyrene, acrylate containing anadamantyl group and acrylate containing a photo-acid generator isdisclosed in US 2007/117043 and Proc. of SPIE, Vol. 6923, 692312, 2008.JP-A-2008-133448 discloses a high energy ray- or heat-sensitive resistcontaining a resin containing a repeating unit capable of generating asulfonic acid at the fluorine-containing terminal of a side chain forimproving high resolution, iso/dense bias and exposure margin.

On the other hand, in electron beam, X-ray or EUV ray lithography, thevolatile constituent from a resist film at exposure time causescontamination of a very expensive exposing apparatus as outed gas.However, if a large amount of a solvent having a high boilingtemperature is used as a resist solvent, the solvent remains in the filmand causes outgassing. Accordingly, the development of a resin componentcapable of dissolving and coating in a general purpose solvent having alow boiling temperature as far as possible is desired.

Thus, it is the present situation that high sensitivity, highresolution, good pattern form, good line edge roughness and outgassingperformance are not sufficiently satisfied at the same time in electronbeam, X-ray or EUV ray lithography by the combinations of the presentlyknown techniques.

In addition, fine processing with a resist composition is not onlydirectly used in the manufacture of integrated circuit but also it isapplied to the manufacture of a mold structure for what is calledimprinting in recent years (e.g., refer to JP-A-2004-158287,JP-A-2008-162101 and Fundamentals, Technical Development and Developmentof Applications of Nano-Imprinting—Techniques on Substrates And TheLatest Technical Development of Nano-Imprinting—, compiled by YoshihikoHirai, published by Frontier Publishing Company (June, 2006)).Therefore, even when X-ray, soft X-ray or electron beam is used as anexposure light source, it is important problems to satisfy highsensitivity, high resolution, good pattern form, good line edgeroughness and outgassing performance at the same time, and resolution ofthese problems is necessary.

SUMMARY OF THE INVENTION

An object of the invention is to provide an actinic ray-sensitive orradiation-sensitive resin composition satisfying high sensitivity, highresolution, good pattern form, good line edge roughness and reduction ofoutgassing at the same time in a super fine region, in particular, inelectron beam, X-ray or EUV ray lithography, and another object is toprovide a pattern-forming method using the same.

It has been found that the above objects are achieved by the followingconstitutions.

<1> An actinic ray-sensitive or radiation-sensitive resin compositioncomprising:

(P) a resin that contains the following repeating units (A), (B) and(C); and

a solvent having a boiling temperature of 150° C. or less,

-   -   (A) a repeating unit containing a group capable of decomposing        and forming an acid upon irradiation with an actinic ray or        radiation,    -   (B) a repeating unit containing a group capable of decomposing        and forming a carboxylic acid by the action of an acid, and    -   (C) a repeating unit containing a carbon-carbon unsaturated        bond.        <2> The actinic ray-sensitive or radiation-sensitive resin        composition as described in <1>, wherein

the repeating unit (B) is a repeating unit represented by the followingformula (I), and

the repeating unit (C) is a repeating unit represented by the followingformula (II):

wherein

each of R₀₁, R₀₂ and R₀₃ independently represents a hydrogen atom, analkyl group, a cycloalkyl group, a halogen atom, a cyano group, or analkoxycarbonyl group, and R₀₃ may represent an alkylene group and bebonded to L or Q to form a 5- or 6-membered ring;

L represents a single bond or a divalent linking group, provided that Lrepresents a trivalent linking group when bonded to R₀₃ to form a 5- or6-membered ring;

R₁ represents an alkyl group;

each of R₂ and R₃ independently represents a hydrogen atom, an alkylgroup, a cycloalkyl group or an aryl group, and R₂ and R₃ may be bondedto each other to form a ring, provided that R₂ and R₃ do not represent ahydrogen atom at the same time; and

Q represents a group containing a carbon-carbon unsaturated bond.

<3> The actinic ray-sensitive or radiation-sensitive resin compositionas described in <1> or <2>, wherein

the compositional amount (mol) of the repeating unit (B) and therepeating unit (C) in the resin (P) satisfies a relationship of therepeating unit (B)≦the repeating unit (C).

<4> The actinic ray-sensitive or radiation-sensitive resin compositionas described in any one of <1> to <3>, wherein

the resin (P) further contains (D) a repeating unit which has a groupcapable of decomposing by the action of an alkali developer andincreasing a dissolution rate in the alkali developer and which isrepresented by the following formula (AII):

wherein

Rb₀ represents a hydrogen atom, a halogen atom or an alkyl group;

Ab represents a single bond, an alkylene group, a divalent linking grouphaving a monocyclic or polycyclic alicyclic hydrocarbon structure, anether bond, an ester bond, a carbonyl group, or a divalent linking groupcombining these; and

V represents a group capable of decomposing by the action of an alkalideveloper and increasing a dissolution rate in the alkali developer.

<5> The actinic ray-sensitive or radiation-sensitive resin compositionas described in any one of <2> to <4>, wherein

Q in formula (II) is a group containing an aromatic ring.

<6> The actinic ray-sensitive or radiation-sensitive resin compositionas described in <5>, wherein

Q in formula (II) is a group containing a benzene ring.

<7> The actinic ray-sensitive or radiation-sensitive resin compositionas described in any one of <1> to <6>, wherein

the resin (P) contains, as the repeating unit (C), a repeating unitderived from hydroxystyrene or a derivative thereof.

<8> The actinic ray-sensitive or radiation-sensitive resin compositionas described in any one of <1> to <7>, wherein

the repeating unit (A) has a structure capable of generating an acidanion on the side chain of the resin upon irradiation with an actinicray or radiation.

<9> The actinic ray-sensitive or radiation-sensitive resin compositionas described in any one of <1> to <8>, wherein

the solvent having a boiling temperature of 150° C. or less is containedin an amount of 65% by mass or more based on all the amount of solvents.

<10> The actinic ray-sensitive or radiation-sensitive resin compositionas described in any one of <1> to <9>, wherein

the solvent having a boiling temperature of 150° C. or less is containedin an amount of 75% by mass or more based on all the amount of solvents.

<11> The actinic ray-sensitive or radiation-sensitive resin compositionas described in any one of <1> to <10>, wherein

the solvent having a boiling temperature of 150° C. or less is containedin an amount of 90% by mass or more based on all the amount of solvents.

<12> The actinic ray-sensitive or radiation-sensitive resin compositionas described in any one of <1> to <11>, wherein

the resin (P) consists of the repeating units (A) to (C) alone or therepeating units (A) to (D) alone, and all of the repeating unit (C) area repeating unit represented by the following formula (II-1):

wherein

Q represents a group containing a carbon-carbon unsaturated bond.

<13> The actinic ray-sensitive or radiation-sensitive resin compositionas described in any one of <1> to <12>, wherein

the proportion of a repeating unit having a cyclic structure in the mainchain in the resin (P) is 30 mol % or less.

<14> The actinic ray-sensitive or radiation-sensitive resin compositionas described in any one of <1> to <13>, wherein

the resin (P) does not contain a repeating unit having a cyclicstructure in the main chain.

<15> The actinic ray-sensitive or radiation-sensitive resin compositionas described in any one of <1> to <14>, wherein

the resin (P) has a weight average molecular weight in the range of1,000 to 100,000.

<16> The actinic ray-sensitive or radiation-sensitive resin compositionas described in any one of <1> to <15>, further comprising:

a basic compound.

<17> The actinic ray-sensitive or radiation-sensitive resin compositionas described in any one of <1> to <16>, which is exposed with anelectron beam, an X-ray or an EUV ray.

<18> A resist film formed with the actinic ray-sensitive orradiation-sensitive resin composition described in any of any one of <1>to <17>.

<19> A pattern-forming method comprising:

exposing and developing the resist film described in <18>.

DETAILED DESCRIPTION OF THE INVENTION

The invention will be described in detail below.

Incidentally, in the description of a group (an atomic group) in thespecification of the invention, the description not referring tosubstitution or unsubstitution includes both a group not having asubstituent and a group having a substituent. For example, “an alkylgroup” includes not only an alkyl group having no substituent (anunsubstituted alkyl group) but also an alkyl group having a substituent(a substituted alkyl group).

“Actinic rays” or “radiations” in the invention means, for example, farultraviolet rays, extreme ultraviolet rays, X-rays, electron means andthe like represented by bright line spectra of mercury lamps and excimerlasers. Further, “light” in the invention means actinic rays orradiations.

Further, “exposure” in the specification includes not only exposure withfar ultraviolet rays, X-rays and EUV rays represented by mercury lampsand excimer lasers but also imaging by corpuscular rays such as electronbeams, ion beams and the like unless otherwise indicated.

The actinic ray-sensitive or radiation-sensitive resin composition inthe invention contains (P) a resin containing repeating units (A), (B)and (C) shown below, and a solvent having a boiling temperature of 150°C. or less:

(A) a repeating unit containing a group capable of decomposing andforming an acid upon irradiation with an actinic ray or radiation,

(B) a repeating unit containing a group capable of decomposing andforming a carboxylic acid by the action of an acid, and

(C) a repeating unit containing a carbon-carbon unsaturated bond.

A repeating unit containing a group capable of decomposing and formingan acid upon irradiation with an actinic ray or radiation and alsocontaining a carbon-carbon unsaturated bond is included in the repeatingunit (A).

As the repeating unit (A), any repeating unit can be used so long as itis a repeating unit capable of decomposing and generating an acid uponirradiation with an actinic ray or radiation, but the repeating unit (A)is preferably a repeating unit having a structure capable of generatingan acid anion on the side chain of the resin upon irradiation with anactinic ray or radiation.

The repeating unit (A) is preferably, for example, a repeating unitrepresented by any of the following formulae (III), (IV) and (V):

In formulae (III) to (V), each of R₀₄, R₀₅, and R₀₇ to R₀₉ independentlyrepresents a hydrogen atom, an alkyl group, a cycloalkyl group, ahalogen atom, a cyano group, or an alkoxycarbonyl group.

R₀₆ represents a hydrogen atom, a cyano group, a carboxyl group,—CO—OR₂₅, or —CO—N(R₂₆)(R₂₇). R₂₆ and R₂₇ may be bonded to form a ringwith a nitrogen atom.

Each of X₁, X₂ and X₃ independently represents a single bond, an arylenegroup, an alkylene group, a cycloalkylene group, —O—, —SO₂—, —CO—,—N(R₃₃)—, or a divalent linking group obtained by combining two or moreof these groups.

R₂₅ represents an alkyl group, a cycloalkyl group, an alkenyl group, anaryl group, or an aralkyl group.

Each of R₂₆, R₂₇ and R₃₃ independently represents a hydrogen atom, analkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or anaralkyl group.

A represents a structural part capable of decomposing and generating anacid upon irradiation with an actinic ray or radiation.

As the alkyl group represented by R₀₄, R₀₅, and R₀₇ to R₀₉ in formulae(III) to (V), substituted or unsubstituted alkyl groups having 20 orless carbon atoms, e.g., a methyl group, an ethyl group, a propyl group,an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group,a 2-ethylhexyl group, an octyl group, and a dodecyl group are preferablyexemplified, and more preferably alkyl groups having 8 or less carbonatoms are exemplified.

As the cycloalkyl group, monocyclic or polycyclic cycloalkyl groups areexemplified. Preferably, substituted or unsubstituted monocycliccycloalkyl groups having 3 to 8 carbon atoms, e.g., a cyclopropyl group,a cyclopentyl group, and a cyclohexyl group are exemplified.

As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom,and an iodine atom are exemplified, and a fluorine atom is morepreferred.

As the alkyl group contained in the alkoxycarbonyl group, the same alkylgroups as in R₀₄, R₀₅, and R₀₇ to R₀₉ are preferred.

As the alkyl group represented by R₂₅ to R₂₇ and R₃₃, substituted orunsubstituted alkyl groups having 20 or less carbon atoms, e.g., amethyl group, an ethyl group, a propyl group, an isopropyl group, ann-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group,an octyl group, and a dodecyl group are preferably exemplified, and morepreferably alkyl groups having 8 or less carbon atoms are exemplified.

As the cycloalkyl group, monocyclic or polycyclic cycloalkyl groups areexemplified. Preferably, substituted or unsubstituted monocycliccycloalkyl groups having 3 to 8 carbon atoms, e.g., a cyclopropyl group,a cyclopentyl group, and a cyclohexyl group are exemplified.

As the alkenyl group, substituted or unsubstituted alkenyl groups having2 to 6 carbon atoms, e.g., a vinyl group, a propenyl group, an allylgroup, a butenyl group, a pentenyl group, a hexenyl group, and acyclohexenyl group are preferably exemplified.

As the aryl group, substituted or unsubstituted monocyclic or polycyclicaromatic groups having 6 to 14 carbon atoms are preferred, andspecifically a phenyl group, a tolyl group, a chlorophenyl group, amethoxyphenyl group, and a naphthyl group are exemplified. Aryl groupsmay be bonded to each other to form a multiple ring.

As the aralkyl group, substituted or unsubstituted aralkyl groups having7 to 15 carbon atoms, e.g., a benzyl group, a phenethyl group and acumyl group are exemplified.

As the ring formed by bonding of R₂₆, and R₂₇ with a nitrogen atom, 5-to 8-membered rings are preferred, and specifically pyrrolidine,piperidine and piperazine are exemplified.

The arylene group represented by each of X₁, X₂ and X₃ is preferably asubstituted or unsubstituted arylene group having 6 to 14 carbon atoms,and specifically a phenylene group, a tolylene group and a naphthylenegroup are exemplified.

The alkylene group may be straight chain or branched. The number ofcarbon atoms of the straight chain alkylene group is preferably 2 to 20,more preferably 3 to 18, and still more preferably 4 to 16. The numberof carbon atoms of the branched alkylene group is preferably 4 to 20,and more preferably 5 to 18. As the specific examples, an ethylenegroup, a propylene group, a butylenes group, a hexylene group, and anoctylene group are exemplified.

As the cycloalkylene group, preferably a substituted or unsubstitutedcycloalkylene group having 5 to 8 carbon atoms, and, e.g., acyclopentylene group and a cyclohexylene group are exemplified.

As the preferred examples of the substituents that each group informulae (III) to (V) may have, a hydroxyl group, a halogen atom (e.g.,fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, anamido group, a sulfonamido group, alkyl groups exemplified in R₀₄ toR₀₉, R₂₅ to R₂₇ and R₃₃, alkoxy groups, e.g., a methoxy group, an ethoxygroup, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group,and a butoxy group, alkoxycarbonyl groups, e.g., a methoxycarbonyl groupand an ethoxycarbonyl group, acyl groups, e.g., a formyl group, anacetyl group and a benzoyl group, acyloxy groups, e.g., an acetoxy groupand a butyryloxy group, and a carboxy group are exemplified. The numberof substituents is preferably 8 or less.

A represents a structural part capable of decomposing and generating anacid upon irradiation with an actinic ray or radiation, specifically aphoto-initiator for cationic photopolymerization, a photo-initiator forradical photopolymerization, a photo-decoloring agent for a dye, aphoto-discoloring agent, and the structural parts of known compoundscapable of generating an acid by the action of a light used inmicro-resist and the like are exemplified.

As the structural part capable of generating an acid anion uponirradiation with an actinic ray or radiation, for example, oniumstructural parts such as a diazonium salt, an ammonium salt, aphosphonium salt, an iodonium salt, a sulfonium salt, a selenonium salt,and an arsonium salt are exemplified.

An ionic structural part containing a sulfonium salt or an iodonium saltis more preferred as A. More specifically, as A capable of generating ananion on the side chain of a resin upon irradiation with an actinic rayor radiation, a group represented by the following formula (ZI) or (ZII)is preferred. In the formulae, the straight lines extending from Z⁻inthe left direction are bonding hands extending toward the main chain ofthe repeating unit (A).

In formula (ZI), each of R₂₀₁, R₂₀₂ and R₂₀₃ independently represents anorganic group.

The number of carbon atoms in the organic group represented by each ofR₂₀₁, R₂₀₂ and R₂₀₃ is generally 1 to 30 and preferably 1 to 20.

Further, two of R₂₀₁, R₂₀₂ and R₂₀₃ may be bonded to each other to forma ring, and an oxygen atom, a sulfur atom, an ester bond, an amido bond,or a carbonyl group may be contained in the ring. As the group formed bytwo of R₂₀₁, R₂₀₂ and R₂₀₃ by bonding, an alkylene group (e.g., abutylene group, a pentylene group) can be exemplified.

Z⁻represents an acid anion decomposed and generated upon irradiationwith an actinic ray or radiation, and a non-nucleophilic anion ispreferred. As the non-nucleophilic anion, e.g., a sulfonate anion, acarboxylate anion, a phosphate anion, a sulfonylimide anion, abis(alkylsulfonyl)imide anion, and a tris(alkylsulfonyl)methyl anion canbe exemplified.

A non-nucleophilic anion is an anion having an extremely low ability ofcausing nucleophilic reaction and capable of inhibiting agingdecomposition by intramolecular nucleophilic reaction. The agingstability of a resin is improved and the aging stability of a resist isalso improved by the presence of such a non-nucleophilic anion.

As the organic group represented by each of R₂₀₁, R₂₀₂ and R₂₀₃, an arylgroup, an alkyl group, a cycloalkyl group, a cycloalkenyl group and anindolyl group are exemplified. Here, in the cycloalkyl group andcycloalkenyl group, at least one of carbon atoms forming a ring may becarbonyl carbon.

It is preferred that at least one of R₂₀₁, R₂₀₂ and R₂₀₃ is an arylgroup, and more preferably all of the three are aryl groups.

As the aryl group represented by each of R₂₀₁, R₂₀₂ and R₂₀₃, a phenylgroup and a naphthyl group are preferred, and a phenyl group is morepreferred.

As the alkyl group, cycloalkyl group and cycloalkenyl group representedby each of R₂₀₁, R₂₀₂ and R₂₀₃, a straight chain or branched alkyl grouphaving 1 to 10 carbon atoms (e.g., a methyl group, an ethyl group, apropyl group, a butyl group, a pentyl group), a cycloalkyl group having3 to 10 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group, anorbonyl group), and a cycloalkenyl group having 3 to 10 carbon atoms(e.g., a cyclopentadienyl group, a cyclohexenyl group) are respectivelyexemplified.

The organic groups such as an aryl group, an alkyl group, a cycloalkylgroup, a cycloalkenyl group and an indolyl group represented by R₂₀₁,R₂₀₂ and R₂₀₃ may further have a substituent. As the substituents, anitro group, a halogen atom, e.g., a fluorine atom, a carboxyl group, ahydroxyl group, an amino group, a cyano group, an alkyl group(preferably having 1 to 15 carbon atoms), an alkoxy group (preferablyhaving 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to15 carbon atoms), an aryl group (preferably having 6 to 14 carbonatoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms),an acyl group (preferably having 2 to 12 carbon atoms), analkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), anarylthio group (preferably having 6 to 14 carbon atoms), a hydroxylalkylgroup (preferably having 1 to 15 carbon atoms), an alkylcarbonyl group(preferably having 2 to 15 carbon atoms), a cycloalkylcarbonyl group(preferably having 4 to 15 carbon atoms), an arylcarbonyl group(preferably having 7 to 14 carbon atoms), a cycloalkenyloxy group(preferably having 3 to 15 carbon atoms), and a cycloalkenylalkyl group(preferably having 4 to 20 carbon atoms) are exemplified, but thesubstituents are not restricted to these groups.

In the cycloalkyl group and cycloalkenyl group as the substituents thateach group represented by R₂₀₁, R₂₀₂ and R₂₀₃ may have, at least one ofcarbon atoms forming a ring may be carbonyl carbon.

Each of the substituents that each group represented by R₂₀₁, R₂₀₂ andR₂₀₃ may have may further have a substituent, and as the examples ofsuch further substituents, the same substituents as described above asthe examples of the substituents that each group represented by R₂₀₁,R₂₀₂ and R₂₀₃ may have can be exemplified, but an alkyl group and acycloalkyl group are preferred.

As preferred structures in the case where at least one of R₂₀₁, R₂₀₂ andR₂₀₃ is not an aryl group, the cationic structures such as the compoundsdisclosed in JP-A-2004-233661, paragraphs [0046] and [0047],JP-A-2003-35948, paragraphs to [0046], the compounds represented byformulae (I-1) to (I-70) in U.S. Patent Application No. 2003/0224288,and the compounds represented by formulae (IA-1) to (IA-54), andformulae (IB-1) to (IB-24) in U.S. Patent Application No. 2003/0077540can be exemplified.

In formula (ZII), each of R₂₀₄ and R₂₀₅ independently represents an arylgroup, an alkyl group or a cycloalkyl group. These aryl, alkyl andcycloalkyl groups are the same as the groups described as the aryl,alkyl and cycloalkyl groups as R₂₀₁, R₂₀₂ and R₂₀₃ in the grouprepresented by formula (ZI).

The aryl group represented by each of R₂₀₄ to R₂₀₇ may be an aryl grouphaving a heterocyclic structure having an oxygen atom, a nitrogen atomor a sulfur atom. As the aryl groups having a heterocyclic structure,for example, a pyrrole residue (a group formed by depriving pyrrole ofone hydrogen atom), a furan residue (a group formed by depriving furanof one hydrogen atom), a thiophene residue (a group formed by deprivingthiophene of one hydrogen atom), an indole residue (a group formed bydepriving indole of one hydrogen atom), a benzofuran residue (a groupformed by depriving benzofuran of one hydrogen atom), and abenzothiophene residue (a group formed by depriving benzothiophene ofone hydrogen atom) can be exemplified.

The aryl group, alkyl group and cycloalkyl group represented by each ofR₂₀₄ and R₂₀₅ may have a substituent. As the substituents, the samegroups as the groups which the aryl group, alkyl group and cycloalkylgroup represented by R₂₀₁ to R₂₀₃ in formula (ZI) may have areexemplified.

Z⁻represents an acid anion decomposed and generated upon irradiationwith an actinic ray or radiation, and a non-nucleophilic anion ispreferred. The same anions as those represented by Z⁻in formula (ZI) areexemplified.

As A capable of generating a cation on the side chain upon irradiationwith an actinic ray or radiation, a group represented by the followingformula (ZCI) or (ZCII) is also preferred. In the formulae, the straightlines extending from s⁺and I⁺in the left direction are bonding handsextending toward the main chain of the repeating unit (A).

In formulae (ZCI) and (ZCII), each of R₃₀₁ and R₃₀₂ independentlyrepresents an organic group.

The number of carbon atoms in the organic group represented by each ofR₃₀₁ and R₃₀₂ is generally 1 to 30 and preferably 1 to 20.

Further, R₃₀₁ and R₃₀₂ may be bonded to each other to form a ring, andan oxygen atom, a sulfur atom, an ester bond, an amido bond, or acarbonyl group may be contained in the ring. As the group formed bybonding of R₃₀₁ and R₃₀₂, an alkylene group (e.g., a butylene group, apentylene group) can be exemplified.

As the organic group represented by R₃₀₁ and R₃₀₂, specifically the arylgroup, alkyl group and cycloalkyl group given as the examples of R₂₀₁ toR₂₀₃ in formula (ZI) can be exemplified.

M⁻represents a non-nucleophilic anion-containing compound, for example,a sulfonate anion-containing compound, a carboxylate anion-containingcompound, a phosphate anion-containing compound, a sulfonylimideanion-containing compound, a bis(alkylsulfonyl)imide anion-containingcompound, and a tris(alkylsulfonyl)methyl anion-containing compound canbe exemplified.

R₃₀₃ represents an organic group. The number of carbon atoms of theorganic group represented by R₃₀₃ is generally 1 to 30 and preferably 1to 20. As the organic group represented by R₃₀₃, specifically the arylgroup, alkyl group and cycloalkyl group shown as the specific examplesof R₂₀₄ and R₂₀₅ in formula (ZII) can be exemplified.

The repeating unit (A) more preferably has a structure capable ofgenerating an acid anion on the side chain of a resin upon irradiationwith an actinic ray or radiation. By selecting such a structure,diffusion of generated acid anion can be restrained and effective fromthe aspect of the improvements of resolution and line edge roughness.

The preferred specific examples of A are shown below but the inventionis by no means limited thereto.

The content of the repeating unit (A) in the resin (P) of the inventionis preferably in the range of 0.5 to 80 mol % of all the repeatingunits, more preferably in the range of 1 to 60 mol %, and especiallypreferably in the range of 2 to 40 mol %. One kind of repeating unit (A)may be used alone, or two or more kinds may be used in combination.

The synthesizing method of a monomer corresponding to repeating unit (A)is not especially restricted but, for example, a synthesizing method ofexchanging an acid anion having a polymerizable unsaturated bondcorresponding to the repeating unit with a halide of a known onium saltcan be exemplified.

More specifically describing, a monomer corresponding to objectiverepeating unit (A) can be synthesized by stirring a metal ion salt of anacid having a polymerizable unsaturated bond corresponding to therepeating unit (e.g., a sodium ion, a potassium ion, etc.) or ammoniumsalt (ammonium, triethyl ammonium, etc.) and an onium salt having ahalogen ion (a chloride ion, a bromide ion, an iodide ion, etc.) in thepresence of water or methanol to perform anion exchange reaction, andthen separating and washing operations with an organic solvent, e.g.,dichloromethane, chloroform, ethyl acetate, methyl isobutyl ketone,tetrahydroxyfuran, or the like, and water.

Further, the monomer can also be synthesized by stirring the abovecompounds in the presence of an organic solvent separable from water,e.g., dichloromethane, chloroform, ethyl acetate, methyl isobutylketone, tetrahydroxyfuran, or the like, and water to perform anionexchange reaction, and then separating and washing operations withwater.

The specific examples of repeating units (A) are shown below, but theinvention is by no means restricted thereto.

Repeating unit (A) may be a repeating unit having a nonionicacid-generating part, such as the exemplified compounds (a31) to (a126)and (a145) to (a196) in JP-A-10-221852.

As the repeating unit (B), any repeating unit can be used so long as itis a repeating unit containing a group capable of decomposing andforming a carboxylic acid by the action of an acid.

A repeating unit represented by the following formula (I) is preferablyused as the repeating unit (B).

In formula (I), each of R₀₁, R₀₂ and R₀₃ independently represents ahydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, acyano group, or an alkoxycarbonyl group. R₀₃ also may represent analkylene group and be bonded to L to form a 5- or 6-membered ring. Lrepresents a single bond or a divalent linking group (provided that Lrepresents a trivalent linking group when bonded to R₀₃ to form a 5- or6-membered ring). R₁ represents an alkyl group, and each of R₂ and R₃independently represents a hydrogen atom, an alkyl group, a cycloalkylgroup or an aryl group. R₂ and R₃ may be bonded to each other to form aring, provided that R₂ and R₃ do not represent a hydrogen atom at thesame time.

As the alkyl group, cycloalkyl group, halogen atom and alkoxycarbonylgroup represented by any of R₀₁ to R₀₃, the same groups as describedabove in R₀₄ to R₀₅ and R₀₇ to R₀₉ can be exemplified.

As the divalent linking group represented by L, an alkylene group, anarylene group, an aralkylene group, —COO—L₁-, —O—L₁-, and a group formedby combining two or more of the above can be exemplified. L₁ representsan alkylene group, a cycloalkylene group, an arylene group, or anaralkylene group.

L preferably represents a single bond, —COO—L₁— (L₁ preferablyrepresents an alkylene group having 1 to 5 carbon atoms, more preferablya methylene group or a propylene group), or an arylene group.

The alkyl group represented by each of R₁ to R₃ is preferably an alkylgroup having 1 to 20 carbon atoms, more preferably an alkyl group having1 to 10 carbon atoms, and especially preferably an alkyl group having 1to 4 carbon atoms, e.g., a methyl group, an ethyl group, an n-propylgroup, an isopropyl group, an n-butyl group, an isobutyl group, or at-butyl group.

The cycloalkyl group represented by each of R₂ and R₃ preferably has 1to 20 carbon atoms, which may be monocyclic such as a cyclopentyl groupor a cyclohexyl group, or may be polycyclic such as a norbonyl group, atetracyclodecanyl group, or a tetracyclododecanyl group, but monocyclicis more preferred from the viewpoint of the solubility in a resistsolvent.

The ring formed by bonding of R₂ and R₃ to each other preferably has 3to 20 carbon atoms, which may be monocyclic such as a cyclopentyl groupor a cyclohexyl group, or may be polycyclic such as a norbonyl group, atetracyclodecanyl group, or a tetracyclododecanyl group, but monocyclicis more preferred from the viewpoint of the solubility in a resistsolvent. When R₂ and R₃ are bonded to each other to form a ring, R₁preferably represents an alkyl group having 1 to 3 carbon atoms, andmore preferably represents a methyl group or an ethyl group.

The aryl group represented by each of R₂ and R₃ preferably has 6 to 20carbon atoms, e.g., a phenyl group and a naphthyl group are exemplified.When either R₂ or R₃ represents a hydrogen atom, another is preferablyan aryl group.

The content of the repeating unit (B) in the resin (P) is preferably inthe range of 5 to 90 mol % of all the repeating units, more preferablyin the range of 10 to 80 mol %, and still more preferably in the rangeof 20 to 70 mol %. One kind of repeating unit (B) may be used alone, ortwo or more kinds may be used in combination.

The synthesizing method of a monomer corresponding to the repeating unit(B) is not especially restricted and ordinary synthesizing methods ofpolymerizable group-containing esters can be used.

The specific examples of repeating units (B) in the resin (P) are shownbelow, but the invention is not restricted thereto.

Any repeating unit can be used as the repeating unit (C) so long as itis a repeating unit containing a carbon-carbon unsaturated bond. Evenwhen repeating unit (A) contains a carbon-carbon unsaturated bond, thiscase is not included in the repeating unit (C). The repeating unit (C)is preferably a repeating unit represented by the following formula(II).

In formula (II), R₀₁, R₀₂ and R₀₃ have the same meaning as described informula (I), and Q represents a group containing a carbon-carbonunsaturated bond. In formula (II), each of R₀₁, R₀₂ and R₀₃ preferablyrepresents a hydrogen atom, and Q preferably represents a groupcontaining an aromatic ring, and more preferably a substituted orunsubstituted aromatic group having 1 to 20 carbon atoms. Here, theexamples of the aromatic groups include the following:

Phenyl, naphthyl, anthranyl, phenanthryl, fluorenyl, triphenylenyl,naphthacenyl, biphenyl, pyrrolinyl, furanyl, thiophenyl, imidazolyl,oxazolyl, thiazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazyl,indolizyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, quinolizyl,quinolinyl, phthalazyl, naphthyridyl, quinoxalyl, quinoxazolyl,isoquinolinyl, carbazolyl, acridyl, phenanthrolyl, thianthrenyl,chromenyl, xanthenyl, phenoxathiinyl, phenothiazyl, and phenazyl. Ofthese aromatic groups, aromatic hydrocarbon rings are preferred, phenyl,naphthyl, anthranyl and phenanthryl are more preferred, and phenyl (abenzene ring) is still more preferred.

When the resin (P) consists of the repeating units (A) to (C) alone, therepeating unit (C) is preferably a repeating unit represented by thefollowing formula (II-1).

Q represents a group containing a carbon-carbon unsaturated bond.

The content of the repeating unit (C) in the resin (P) is preferably inthe range of 5 to 90 mol % to all the repeating units, more preferablyin the range of 10 to 80 mol %, and still more preferably in the rangeof 20 to 70 mol %. One kind of repeating unit (C) may be used alone, ortwo or more kinds may be used in combination, but it is preferred tocontain at least one kind of repeating unit derived from hydroxystyrene(preferably p-hydroxystyrene) and derivatives thereof. As thehydroxystyrene derivatives, for example, hydroxystyrenes containingfluorine-substituted alcohol-substituted groups are exemplified.

In the invention, the compositional ratio of the repeating unit (C)(mol) is preferably equal to or higher than the compositional ratio ofthe repeating unit (B). Here, of the repeating units (B), repeatingunits having a carbon-carbon unsaturated bond are also included in therepeating unit (C).

The synthesizing method of monomers corresponding to the repeating unit(C) is not especially restricted, but the monomers can be synthesized byreferring to the synthesizing methods of aromatic compounds containing apolymerizable carbon-carbon double bond described in, for example, J.Med. Chem., Vol. 34 (5), 1675-1692 (1991), ditto, Vol. 35 (25),4665-4675 (1992), J. Org. Chem., Vol. 45 (18), 3657-3664 (1980), Adv.Synth. Catal., Vol. 349 (1-2), 152-156 (2007), J. Org. Chem., Vol. 28,1921-1922 (1963), Synth. Commun., Vol. 28 (15), 2677-2682 (1989), andthe synthesizing methods cited in these documents.

The specific examples of repeating units (C) in the resin (P) are shownbelow, but the invention is not restricted thereto. In the formulae, arepresents an integer of 0 to 2.

It is preferred for the resin in the invention to further contain (D) arepeating unit which has a group capable of decomposing by the action ofan alkali developer and increasing a dissolution rate in the alkalideveloper and which is represented by the following formula (AII).

In formula (AII), Rb₀ represents a hydrogen atom, a halogen atom, or analkyl group (preferably having 1 to 4 carbon atoms).

As preferred substituents that the alkyl group represented by Rb₀ mayhave, a hydroxyl group and a halogen atom are exemplified. As theexamples of the halogen atoms represented by Rb₀, a fluorine atom, achlorine atom, a bromine atom and an iodine atom are exemplified. Thepreferred are a hydrogen atom, a methyl group, a hydroxymethyl group,and a trifluoromethyl group, and a hydrogen atom and a methyl group areespecially preferred.

Ab represents a single bond, an alkylene group, a divalent linking grouphaving a monocyclic or polycyclic alicyclic hydrocarbon structure, anether bond, an ester bond, a carbonyl group, or a divalent linking groupcombining these groups, and preferably a single bond or a divalentlinking group represented by -Ab₁-CO₂—.

Ab₁ represents a straight chain or branched alkylene group, or amonocyclic or polycyclic cycloalkylene group, and preferably a methylenegroup, an ethylene group, a cyclohexylene group, an adamantylene group,or a norbornylene group.

V represents a group capable of decomposing by the action of an alkalideveloper and increasing a dissolution rate in the alkali developer,preferably a group having an ester bond, and more preferably a grouphaving a lactone structure.

As groups having a lactone structure, any group having a lactonestructure can be used, but preferably groups having 5- to 7-memberedring lactone structures, and 5- to 7-membered ring lactone structurescondensed with other ring structures in the form of forming a bicyclostructure or a spiro structure are preferred. It is more preferred tohave a repeating unit having lactone structure represented by any of thefollowing formulae (LC1-1) to (LC1-17). A lactone structure may bedirectly bonded to the main chain. Preferred lactone structures are(LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14) and (LC1-17).

The lactone structural part may have or may not have a substituent(Rb₂). As preferred substituents (Rb₂), an alkyl group having 1 to 8carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxylgroup having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, acyano group, and an acid-decomposable group are exemplified, and morepreferred substituents are an alkyl group having 1 to 4 carbon atoms, acyano group, and an acid-decomposable group. n₂ represents an integer of0 to 4. When n₂ is 2 or more, each substituent may be the same with ordifferent from every other substituent. A plurality of substituents(Rb₂) may be bonded to each other to form a ring.

Repeating units having a lactone structure generally have opticalisomers, and any optical isomer may be used. One kind of optical isomermay be used alone, or a plurality of optical isomers may be used asmixture. When one kind of optical isomer is mainly used, optical purity(ee) is preferably 90% or more and more preferably 95% or more.

The content of the repeating unit (D) in the resin (P) is preferably inthe range of 0.5 to 80 mol % to all the repeating units, more preferablyin the range of 1 to 60 mol %, and still more preferably in the range of2 to 40 mol %. One kind of repeating unit (D) may be used alone, or twoor more kinds may be used in combination. By the use of a specificlactone structure, line edge roughness and development defect arebettered.

The specific examples of repeating units (D) in the resin (P) are shownbelow, but the invention is not restricted thereto. In the formulae, Rxrepresents H, CH₃, CH₂OH or CF₃.

The form of the resin (P) of the invention may be any type of random,block, comb and star types.

The resin (P) according to the invention containing repeating units (A)to (C) or (A) to (D) can be synthesized by, for example, radicalpolymerization, cationic polymerization, or anionic polymerization ofunsaturated monomer corresponding to each structure. It is also possibleto obtain an objective resin by polymerization with an unsaturatedmonomer corresponding to precursor of each structure, and then byperforming polymeric reaction.

The molecular weight of the resin (P) in the invention is not especiallyrestricted, but the weight average molecular weight is preferably in therange of 1,000 to 100,000, more preferably in the range of 1,500 to20,000, and especially preferably in the range of 2,000 to. 10,000. Theweight average molecular weight of the resin here shows the polystyreneequivalent molecular weight measured by GPC (carrier: THF orN-methyl-2-pyrrolidone (NMP)).

Polydispersity (Mw/Mn) is preferably 1.00 to 5.00, more preferably 1.03to 3.50, and still more preferably 1.05 to 2.50.

For the purpose of improving the performances of resin, the resin (P) ofthe invention may further contain repeating units derived from otherpolymerizable monomers so long as dry etching resistance is notconspicuously damaged.

The content of repeating units derived from other polymerizable monomersin the resin is generally 50 mol % or less of all the repeating unitsand preferably 30 mol % or less. As other usable polymerizable monomers,the following are included. For example, the polymerizable monomersinclude compounds having one addition polymerizable unsaturated bondselected from (meth)acrylates, (meth)acrylamides, allyl compounds, vinylethers, vinyl esters, styrenes, and crotonates.

Specifically, as (meth)acrylates, e.g., methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, t-butyl(meth)acrylate,amyl(meth)acrylate, cyclohexyl(meth)acrylate, ethylhexyl(meth)acrylate,octyl(meth)acrylate, t-octyl (meth)acrylate,2-chloroethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, glycidyl(meth)acrylate, benzyl(meth)acrylate, and phenyl(meth)acrylate areexemplified.

As (meth)acrylamides, e.g., (meth)acrylamide, N-alkyl(meth)acrylamide(as the alkyl group, an alkyl group having 1 to 10 carbon atoms, e.g., amethyl group, an ethyl group, a propyl group, a butyl group, a t-butylgroup, a heptyl group, an octyl group, a cyclohexyl group, a benzylgroup, a hydroxyethyl group, a benzyl group, etc.),N-aryl(meth)acrylamide (as the aryl group, e.g., a phenyl group, a tolylgroup, a nitrophenyl group, a naphthyl group, a cyanophenyl group, ahydroxyphenyl group, a carboxyphenyl group, etc.),N,N-dialkyl(meth)acrylamide (as the alkyl group, an alkyl group having 1to 10 carbon atoms, e.g., a methyl group, an ethyl group, a butyl group,an isobutyl group, an ethylhexyl group, a cyclohexyl group, etc.),N,N,-aryl-(meth)acrylamide (as the aryl group, e.g., a phenyl group),N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, andN-2-acetamidoethyl-N-acetyl-acrylamide are exemplified.

As allyl compounds, e.g., allyl esters (e.g., allyl acetate, allylcaproate, allyl caprylate, allyl laurate, allyl palmitate, allylstearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), andallyloxy ethanol are exemplified.

As vinyl ethers, e.g., alkyl vinyl ether (e.g., hexyl vinyl ether, octylvinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethylvinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether,1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether,hydroxyethyl vinyl ether, diethylene glycol vinyl ether,dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether,butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfurylvinyl ether, etc.), and vinyl aryl ether (e.g., vinyl phenyl ether,vinyl tolyl ether, vinyl chlorophenyl ether, vinyl 2,4-dichlorophenylether, vinyl naphthyl ether, vinyl anthranyl ether, etc.) areexemplified.

As vinyl esters, e.g., vinyl butyrate, vinyl isobutyrate, vinyltrimethylacetate, vinyl diethylacetate, vinyl valate, vinyl caproate,vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinylbutoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate,vinyl β-phenylbutyrate, vinyl cyclohexylcarboxylate, vinyl benzoate,vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinylnaphthoate, etc., are exemplified.

As crotonates, e.g., alkyl crotonate (e.g., butyl crotonate, hexylcrotonate, glycerol monocrotonate, etc.) are exemplified.

As dialkyl itaconates, e.g., dimethyl itaconate, diethyl itaconate,dibutyl itaconate, etc., are exemplified.

As dialkyl esters of maleic acid or fumaric acid, e.g., dimethylmaleate, dibutyl fumarate, etc., are exemplified.

Besides the above, maleic anhydride, maleimide, acrylonitrile,methacrylonitrile, and maleilonitrile can be exemplified. Further,addition polymerizable unsaturated compounds capable of copolymerizationwith the repeating units according to the invention can be used with noparticular limitation.

The resin (P) of the invention may be one kind alone, or two or morekinds may be used in combination. The content of the resin (P) ispreferably 30 to 100% by mass based on all the solids content in theactinic ray-sensitive or radiation-sensitive resin composition of theinvention, more preferably 50 to 100% by mass, and especially preferably70 to 100% by mass.

As the specific examples of the resin (P), resins having one or morerepeating units selected from resins having one or more repeating unitsselected from the specific examples of formulae (III) to (V)/one or morerepeating units selected from the specific examples of formula (I)/oneor more repeating units selected from the specific examples of formula(II) are exemplified.

In particular, it is preferred that the resin (P) consists of therepeating units (A) to (C) alone or the repeating units (A) to (D)alone, and all of the repeating unit (C) are the repeating unitrepresented by formula (II-1). The repeating unit (C) may comprise oneor more repeating units represented by formula (II-1).

Also in the resin (P), it is preferred that the proportion of therepeating unit having a cyclic structure in the main chain is 30 mol %or less, and it is more preferred not to contain the repeating unit atall.

More preferred specific examples of resins (P) are shown below but theinvention is not restricted thereto.

The actinic ray-sensitive or radiation-sensitive resin composition inthe invention contains a solvent having a boiling temperature of 150° C.or less at normal pressure (760 mmHg).

A solvent having a boiling temperature of 150° C. or less at normalpressure may be used alone, or two or more kinds may be used incombination. Further, a solvent having a boiling temperature exceeding150° C. at normal pressure may be used in combination. In thecomposition of the invention, the content of a solvent having a boilingtemperature of 150° C. or less is preferably 50% by mass or more of allthe amount of solvents, more preferably 65% by mass or more, still morepreferably 70 to 100% by mass, especially preferably 75% by mass ormore, and most preferably 90% by mass or more.

The boiling temperature of a solvent having a boiling temperature of150° C. or less is preferably 50 to 150° C., and more preferably 80 to150° C.

A solvent having a boiling temperature of 150° C. or less is preferablyan organic solvent, and such a solvent can be selected from, forexample, alkylene glycol monoalkyl ether carboxylate, alkylene glycolmonoalkyl ether, alkyl lactate ester, alkylalkoxy propionate, cycliclactone, a monoketone compound which may have a ring, alkylenecarbonate, alkylalkoxy acetate, and alkyl pyruvate.

For example, a solvent having a boiling temperature of 150° C. or lessat normal pressure is selected from the following exemplified solventsand one kind alone or two or more kinds may be used as mixture, further,such a solvent may be used in combination with a solvent having aboiling temperature exceeding 150° C. at normal pressure. Incidentally,in connecting with the following exemplified solvents, when there is nodescription about the pressure, the boiling temperature is the one atnormal pressure. Further, when the boiling temperature at pressure otherthan 760 mmHg is described, it means that the solvent is a solventhaving a high boiling temperature, and the solvent shows a boilingtemperature higher than 150° C. at 760 mmHg.

As alkylene glycol monoalkyl ether carboxylate, e.g., propylene glycolmonomethyl ether acetate (PGMEA, 1-methoxy-2-acetoxypropane) (b.p.: 146°C.), propylene glycol monoethyl ether acetate (b.p.: 164-165° C.),propylene glycol monopropyl ether acetate (b.p.: 173-174° C./740 mmHg),ethylene glycol monomethyl ether acetate (b.p.: 143° C.), and ethyleneglycol monoethyl ether acetate (b.p.: 156° C.) are preferablyexemplified.

As alkylene glycol monoalkyl ether, e.g., propylene glycol monomethylether (PGME, 1-methoxy-2-propanol) (b.p.: 119° C.), propylene glycolmonoethyl ether (b.p.: 130-131° C.), propylene glycol monopropyl ether(b.p.: 148° C.), propylene glycol monobutyl ether (b.p.: 169-170° C.),ethylene glycol monomethyl ether (b.p.: 124-125° C.), and ethyleneglycol monoethyl ether (b.p.: 134-135° C.) are preferably exemplified.

As alkyl lactate ester, e.g., methyl lactate (b.p.: 145° C.), ethyllactate (b.p.: 154° C.), propyl lactate (b.p.: 169-172° C.), and butyllactate (b.p.: 185-187° C.) are preferably exemplified.

As alkylalkoxy propionate, e.g., ethyl-3-ethoxy propionate (b.p.:169-170° C.), methyl-3-ethoxy propionate (b.p.: 138-141° C.), andethyl-3-methoxy propionate (b.p.: 156-158° C.) are preferablyexemplified.

As cyclic lactone, e.g., β-propiolactone (b.p.: 162° C.),β-butyrolactone (b.p.: 71-73° C./29 mmHg), γ-butyrolactone (b.p.:204-205° C.), α-methyl-γ-butyrolactone (b.p.: 78-81° C./10 mmHg),β-methyl-γ-butyrolactone (b.p.: 87-88° C./10 mmHg), γ-valerolactone(b.p.: 82-85° C./10 mmHg), γ-caprolactone (b.p.: 219° C.), γ-octanoiclactone (b.p.: 234° C.), and α-hydroxy-γ-butyrolactone (b.p.: 133° C./10mmHg) are preferably exemplified.

As monoketone compounds which may have a ring, e.g., 2-butanone (b.p.:80° C.), 3-methylbutanone (b.p.: 94-95° C.), pinacolone (b.p.: 106° C.),2-pentanone (b.p.: 101-105° C.), 3-pentanone (b.p.: 102° C.),3-methyl-2-pentanone (b.p.: 118° C.), 4-methyl-2-pentanone (b.p.:117-118° C.), 2-methyl-3-pentanone (b.p.: 113° C.),4,4-dimethyl-2-pentanone (b.p.: 125-130° C.), 2,4-dimethyl-3-pentanone(b.p.: 124° C.), 2,2,4,4-tetramethyl-3-pentanone (b.p.: 152-153° C.),2-hexanone (b.p.: 127° C.), 3-hexanone (b.p.: 123° C.),5-methyl-2-hexanone (b.p.: 145° C.), 2-heptanone (b.p.: 149-150° C.),3-heptanone (b.p.: 146-148° C.), 4-heptanone (b.p.: 145° C.),2-methyl-3-heptanone (b.p.: 158-160° C.), 5-methyl-3-heptanone (b.p.:161-162° C.), 2,6-dimethyl-4-heptanone (b.p.: 165-170° C.), 2-octanone(b.p.: 173° C.), 3-octanone (b.p.: 167-168° C.), 2-nonanone (b.p.: 192°C./743 mmHg), 3-nonanone (b.p.: 187-188° C.), 5-nonanone (b.p.: 186-187°C.), 2-decanone (b.p.: 211° C.), 3-decanone (b.p.: 204-205° C.),4-decanone (b.p.: 206-207° C.), 5-hexen-2-one (b.p.: 128-129° C.),3-penten-2-one (b.p.: 121-124° C.), cyclopentanone (b.p.: 130-131° C.),2-methylcyclopentanone (b.p.: 139° C.), 3-methylcyclopentanone (b.p.:145° C.), 2,2-dimethylcyclopentanone (b.p.: 143-145° C.),2,4,4-trimethylcyclopentanone (b.p.: 160° C.), cyclohexanone (b.p.: 157°C.), 3-methylcyclohexanone (b.p.: 169-170° C.), 4-methylcyclohexanone(b.p.: 169-171° C.), 4-ethylcyclohexanone (b.p.: 192-194° C.),2,2-dimethylcyclohexanone (b.p.: 169-170° C.), 2,6-dimethylcyclohexanone(b.p.: 174-176° C.), 2,2,6-trimethylcyclohexanone (b.p.: 178-179° C.),cycloheptanone (b.p.: 179° C.), 2-methylcycloheptanone (b.p.: 182-185°C.), and 3-methylcycloheptanone (b.p.: 100° C./40 mmHg) are preferablyexemplified.

As alkylene carbonate, e.g., propylene carbonate (b.p.: 240° C.),vinylene carbonate (b.p.: 162° C.), ethylene carbonate (b.p.: 243-244°C./740 mmHg), an butylene carbonate (b.p.: 88° C./0.8 mmHg) arepreferably exemplified.

As alkylalkoxy acetate, e.g., 2-methoxyethyl acetate (b.p.: 145° C.),2-ethoxyethyl acetate (b.p.: 155-156° C.), 2-(2-ethoxyethoxy)ethylacetate (b.p.: 219° C.), and 1-methoxy-2-propyl acetate (b.p.: 145-146°C.) are preferably exemplified.

As alkyl pyruvate, e.g., methyl pyruvate (b.p.: 134-137° C.), ethylpyruvate (b.p.: 144° C.), and propyl pyruvate (b.p.: 166° C.) arepreferably exemplified.

As preferably usable solvents, 2-heptanone, cyclopentanone,γ-butyrolactone, cyclohexanone, butyl acetate, ethyl lactate, ethyleneglycol monoethyl ether acetate, propylene glycol monomethyl etheracetate, propylene glycol monomethyl ether, ethyl-3-ethoxy propionate,ethyl pyruvate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate,and propylene carbonate are exemplified, but from the viewpoint of thereduction of outgassing, solvents whose boiling temperature is 150° C.or less at normal pressure such as 2-heptanone, propylene glycolmonomethyl ether acetate, and propylene glycol monomethyl ether areespecially preferred.

The use amount of the solvent (including all the solvents having aboiling temperature of 150° C. or more and 150° C. or less) in the wholeamount of the composition can be arbitrarily adjusted according to adesired film thickness and the like, but is generally adjusted so thatthe concentration of the entire solids content of the compositionreaches 0.5 to 30% by mass, preferably 1.0 to 20% by mass, and morepreferably 1.5 to 10% by mass.

The actinic ray-sensitive or radiation-sensitive resin composition inthe invention can further contain, according to necessity, a basiccompound, a resin capable of decomposing by the action of an acid toincrease a dissolution rate in an alkali aqueous solution, aconventional photo-acid generator, a surfactant, an acid-decomposabledissolution-inhibiting compound, a dye, a plasticizer, aphoto-sensitizer, a dissolution-accelerating compound in a developer,and a compound having a proton-accepting functional group.

<Basic Compounds>

It is preferred that the actinic ray-sensitive or radiation-sensitiveresin composition in the invention further contains a basic compound.

The basic compound is preferably a nitrogen-containing organic basiccompound.

Usable compounds are not especially limited and, for example, compoundsclassified into the following (1) to (4) are preferably used.

(1) Compound Represented by the Following Formula (BS-1)

In formula (BS-1), each of R independently represents any of a hydrogenatom, an alkyl group (straight chain or branched), a cycloalkyl group(monocyclic or polycyclic), an aryl group, and an aralkyl group.However, not all of three R's represent a hydrogen atom.

The carbon atom number of the alkyl group represented by R is notespecially restricted and is generally 1 to 20, and preferably 1 to 12.

The carbon atom number of the cycloalkyl group represented by R is notespecially restricted and is generally 3 to 20, and preferably 5 to 15.

The carbon atom number of the aryl group represented by R is notespecially restricted and is generally 6 to 20, and preferably 6 to 10.Specifically a phenyl group and a naphthyl group are exemplified.

The carbon atom number of the aralkyl group represented by R is notespecially restricted and is generally 7 to 20, and preferably 7 to 11.Specifically a benzyl group is exemplified.

The hydrogen atom of each of the alkyl group, cycloalkyl group, arylgroup and aralkyl group represented by R may be substituted with asubstituent. As the substituents, an alkyl group, a cycloalkyl group, anaryl group, an aralkyl group, a hydroxyl group, a carboxyl group, analkoxy group, an aryloxy group, an alkylcarbonyloxy group, and analkylcarbonyl group are exemplified.

It is preferred that, in the compound represented by formula (BS-1), onealone of three R's represents a hydrogen atom, or all R are not hydrogenatoms.

As the specific examples of the compound represented by formula (BS-1),tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine,triisodecylamine, dicyclohexylmethylamine, tetradecylamine,pentadecylamine, hexadecylamine, octadecylamine, didecylamine,methyloctadecylamine, dimethylundecylamine, N,N-dimethyldodecylamine,methyldioctadecylamine, N,N-dibutylaniline, N,N-dihexylaniline,2,6-diisopropylaniline, and 2,4,6-tri(t-butyl)aniline are exemplified.

Further, in formula (BS-1), a compound in which at least one R is analkyl group substituted with a hydroxyl group is exemplified as apreferred embodiment. As the specific compounds, triethanolamine andN,N-dihydroxyethylaniline are exemplified.

Further, the alkyl group represented by R may have an oxygen atom in thealkyl chain to form an oxyalkylene chain. As the oxyalkylene chain,—CH₂CH₂O— is preferred. As the specific examples,tris(methoxyethoxyethyl)amine and the compounds disclosed in U.S. Pat.No. 6,040,112, column 3, line 60 and after, are exemplified.

(2) Compound Having a Nitrogen-Containing Heterocyclic Structure

As the heterocyclic structure, the compound may have or may not have anaromatic property. Further, a plurality of nitrogen atoms may becontained, and hetero atoms other than nitrogen atom may be contained.Specifically, a compound having an imidazole structure, (e.g.,2-phenylbenzimidazole, 2,4,5-triphenylimidazole), a compound having apiperidine structure (e.g., N-hydroxyethylpiperidine,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate), a compound having apyridine structure (e.g., 4-dimethylaminopyridine), and a compoundhaving an antipyrine structure (e.g., antipyrine, hydroxyantipyrine) areexemplified.

A compound having two or more cyclic structures is also preferably used.Specifically, 1,5-diazabicyclo[4.3.0]non-5-ene,1,8-diazabicyclo[5.4.0]undeca-7-ene are exemplified.

(3) Amine Compound Having a Phenoxy Group

An amine compound having a phenoxy group is a compound having a phenoxygroup at the terminal on the opposite side to the nitrogen atom of thealkyl group of an amine compound. The phenoxy group may have asubstituent, e.g., an alkyl group, an alkoxy group, a halogen atom, acyano group, a nitro group, a carboxyl group, a carboxylic acid estergroup, a sulfonic acid ester group, an aryl group, an aralkyl group, anacyloxy group, or an aryloxy group.

More preferably, the compound is a compound having at least oneoxyalkylene chain between the phenoxy group and the nitrogen atom. Thenumber of oxyalkylene chains in one molecule is preferably 3 to 9, andmore preferably 4 to 6. Of oxyalkylene chains, —CH₂CH₂O— is preferred.

As the specific examples,2-[2-{2-(2,2-dimethoxyphenoxyethoxy)ethyl}-bis(2-methoxyethyl)]amine,and Compounds (C1-1) to (C1-3) disclosed in U.S. Patent Application No.2007/0224539A1, paragraph [0066] are exemplified.

(4) Ammonium Salt

Ammonium salts are also arbitrarily used. Preferred compound ishydroxide or carboxylate. More specifically, tetraalkylammoniumhydroxide represented by tetrabutylammonium hydroxide is preferred.

As other basic compounds, the compounds synthesized in JP-A-2002-363146and the compounds disclosed in JP-A-2007-298569, paragraph [0108] canalso be used.

Basic compounds are used alone or in combination of two or more.

The use amount of basic compounds is generally 0.001 to 10% by massbased on all the solid content of the actinic ray-sensitive orradiation-sensitive resin composition, and preferably 0.01 to 5% bymass.

The molar ratio of acid generator/basic compound is preferably 2.5 to300. That is, the molar ratio of 2.5 or more is preferred from the pointof sensitivity and resolution, and 300 or less is preferred from thepoint of inhibition of the reduction of resolution by the thickening ofthe pattern in aging after exposure until heat treatment. The molarratio is more preferably 5.0 to 200 and still more preferably 7.0 to150.

The acid generator in the above molar ratio is the amount of sum totalof repeating unit (a) contained in the resin (P) and the later-describedacid generator other than the resin (P).

<Resin Capable of Decomposing by the Action of an Acid to Increase aDissolution Rate in an Alkali Aqueous Solution>

The actinic ray-sensitive or radiation-sensitive resin composition inthe invention may contain a resin capable of decomposing by the actionof an acid to increase a dissolution rate in an alkali aqueous solutionbesides the resin (P).

A resin capable of decomposing by the action of an acid to increase adissolution rate in an alkali aqueous solution (hereinafter referred toas “acid-decomposable resin”) is a resin having a group capable ofdecomposing by the action of an acid and generating an alkali-solublegroup (acid-decomposable group) on the main chain or side chain of aresin, or both main chain and side chain. A resin having anacid-decomposable group on the side chain is more preferred.

As disclosed in European Patent No. 254853, JP-A-2-25850, JP-A-3-223860and JP-A-4-251259, acid-decomposable resin can be obtained by reactingan alkali-soluble resin with a precursor of acid-decomposable group, orby copolymerizing an alkali-soluble resin monomer with various monomers.

As acid-decomposable group, e.g., a group obtained by substituting thehydrogen atom of an alkali-soluble group, an alkali-soluble group suchas a —COO group or an —OH group in a resin having the alkali-solublegroup, with a group capable of leaving by the action of an acid ispreferred.

As acid-decomposable groups, specifically the same groups with theacid-decomposable groups described above in the resin of the invention(e.g., acid-decomposable groups described as the repeating unit (B) inthe resin (P)) can be preferably exemplified.

The alkali-soluble resin is not especially restricted. For example,alkali-soluble resins having a hydroxystyrene structure, e.g.,poly(o-hydroxystyrene), poly(m-hydroxystyrene), poly(p-hydroxystyrene),copolymers thereof, hydrogenated poly(hydroxystyrene),poly(hydroxystyrenes) having the substituent represented by any of thestructures shown below, a resin having a phenolic hydroxyl group, astyrene-hydroxystyrene copolymer, an α-methylstyrene-hydroxystyrenecopolymer, and hydrogenated novolak resin, and alkali-soluble resinscontaining a repeating unit having a carboxyl group such as(meth)acrylic acid or norbornene carboxylic acid are exemplified.

The alkali dissolution rate of these alkali-soluble resins is preferably170 Å/sec or more particularly preferably 330 Å/sec or more, whenmeasured with a 2.38% by mass of tetramethylammonium hydroxide (TMAH) at23° C. More specifically, the alkali dissolution rate can be obtained bydissolving an alkali-soluble resin alone in a solvent such as propyleneglycol monomethyl ether acetate (PGMEA) to make a composition havingsolid content concentration of 4% by mass, coating the composition on asilicon wafer to make a film (thickness: 100 nm), and measuring the time(seconds) until the film is thoroughly dissolved in a TMAH aqueoussolution.

The content of an acid-decomposable group is expressed by the equationof X/(X+Y) taking the number of repeating units having a group capableof decomposing by the action of an acid in a resin as (X), and thenumber of repeating units having an alkali-soluble group not protectedwith a group capable of leaving by the action of an acid as (Y). Thecontent is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, andstill more preferably 0.05 to 0.40.

The weight average molecular weight of acid-decomposable resins ispreferably 50,000 or less as the polystyrene equivalent by GPC method,more preferably 1,000 to 20,000, and especially preferably 1,000 to10,000.

The polydispersity (Mw/Mn) of acid-decomposable resins is preferably 1.0to 3.0, more preferably 1.05 to 2.0, and still more preferably 1.1 to1.7.

Two or more acid-decomposable resins may be used in combination.

In the actinic ray-sensitive or radiation-sensitive resin composition inthe invention, the blending amount of acid-decomposable resins in thecomposition exclusive of the resin (P) is preferably 0 to 70% by mass inall the solids content of the composition, more preferably 0 to 50% bymass, and still more preferably 0 to 30% by mass.

<Acid-Generators>

The actinic ray-sensitive or radiation-sensitive resin composition inthe invention contains the resin (P) having a photo-acid generatingstructure, and the composition may contain, other than the resin (P), alow molecular weight compound capable of generating an acid uponirradiation with an actinic ray or radiation (hereinafter also referredto as “acid-generator”)

As such acid-generators, a photo-initiator for cationicphotopolymerization, a photo-initiator for radical photopolymerization,a photo-decoloring agent for a dye, a photo-discoloring agent, and knowncompounds capable of generating an acid upon irradiation with an actinicray or radiation, and mixtures thereof can be arbitrarily selected andused.

For example, a diazonium salt, a phosphonium salt, a sulfonium salt, aniodonium salt, imidosulfonate, oximsulfonate, diazodisulfone, disulfone,and o-nitrobenzyl sulfonate can be exemplified. As the specific examplesof them, the compounds disclosed in U.S. Patent Application2008/0241737A1, paragraphs [0164] to [0248] can be referred to.

When acid-generators are used in the actinic ray-sensitive orradiation-sensitive resin composition in the invention other than theresin (P) having a photo-acid generating structure, the acid-generatorsmay be one kind alone, or two or more kinds may be used in combination.The content of acid-generators in the composition is preferably 0 to 20%by mass based on all the solids content in the resist composition, morepreferably 0 to 10% by mass, and still more preferably 0 to 7% by mass.Acid-generators are not essential in the invention, but for obtainingthe effect of addition, they are used in an amount of generally 0.01% bymass or more.

<Surfactants>

It is preferred for the actinic ray-sensitive or radiation-sensitiveresin composition in the invention to further contain a surfactant. Asthe surfactants, fluorine/silicon surfactants are preferred.

As such surfactants, MEGAFAC F176, MEGAFAC R08 (manufactured byDainippon Ink and Chemicals Inc.), PF656, PF6320 (manufactured by OMNOVASolution Inc.), Troy Sol S-366 (manufactured by Troy Chemical Co.,Ltd.), Fluorad FC430 (manufactured by Sumitomo 3M Limited), andpolysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co.,Ltd.) are exemplified.

It is also possible to use surfactants other than fluorine/siliconsurfactants. More specifically, polyoxyethylene alkyl ethers andpolyoxyethylene alkylaryl ethers are exemplified.

In addition to the above, known surfactants can be optionally used. Asother usable surfactants, the surfactants disclosed in U.S. PatentApplication No. 2008/0248425A1, paragraphs from [0273] downward areexemplified.

Surfactants may be used alone, or two or more may be used incombination.

The use amount of surfactants is preferably 0.0001 to 2% by mass basedon all the solids content of the actinic ray-sensitive orradiation-sensitive resin composition, and more preferably 0.001 to 1%by mass.

<Acid-Decomposable Dissolution-Inhibiting Compounds>

The actinic ray-sensitive or radiation-sensitive resin composition inthe invention can contain a dissolution-inhibiting compound capable ofdecomposing by the action of an acid to increase a dissolution rate in adeveloper having a molecular weight of 3,000 or less (hereinafter alsoreferred to as “a dissolution-inhibiting compound”).

As the dissolution-inhibiting compounds, alicyclic or aliphaticcompounds having an acid-decomposable group, such as a cholic acidderivative containing an acid-decomposable group described in Proceedingof SPIE, 2724, 355 (1996) are preferred. As acid-decomposable groups andalicyclic structures, the same compounds as described above in theacid-decomposable resins can be exemplified.

When the actinic ray-sensitive or radiation-sensitive resin compositionin the invention is irradiated with an electron beam or EUV ray, adissolution-inhibiting compound having such a structure that thephenolic hydroxyl group of a phenol compound is substituted with anacid-decomposable group is preferably used. As the phenol compound,those having 1 to 9 phenol structures is preferred, and more preferablyhaving 2 to 6 phenol structures.

The molecular weight of the dissolution-inhibiting compound in theinvention is 3,000 or less, preferably 300 to 3,000, and more preferably500 to 2,500.

<Other Components>

The actinic ray-sensitive or radiation-sensitive resin composition inthe invention may contain a dye. Oil dyes and basic dyes are preferred.

For increasing acid-generating efficiency by exposure, the actinicray-sensitive or radiation-sensitive resin composition in the inventioncan further contain a photo-sensitizer.

Dissolution-accelerating compounds in a developer usable in theinvention are low molecular weight compounds having 2 or more phenolichydroxyl groups or 1 or more carboxyl groups, and a molecular weight of1,000 or less. When the compounds have carboxyl groups, alicyclic oraliphatic compounds are preferred. Such phenol compounds having amolecular weight of 1,000 or less are disclosed, e.g., in JP-A-4-122938,JP-A-2-28531, U.S. Pat. No. 4,916,210 and European Patent 219,294.

The compounds having a proton-accepting functional group disclosed inJP-A-2006-208781 and JP-A-2007-286574 can also be preferably used in thecomposition of the invention.

<Pattern-Forming Method>

The actinic ray-sensitive or radiation-sensitive resin composition inthe invention is coated on a support such as a substrate and a resistfilm is formed. The thickness of the resist film is preferably 0.02 to0.1 μm.

As a method of coating on a substrate, spin coating is preferred, andthe number of revolution is preferably 1,000 to 3,000 rpm.

The actinic ray-sensitive or radiation-sensitive resin composition iscoated on a substrate such as the one used in manufacture of a fineintegrated circuit device (e.g., silicon, silicon dioxide coating) by aproper coating method, e.g., with a spinner, a coater or the like. Thecoated substrate is then dried to form a resist film. A knownantireflection film may be previously coated.

The resist film is subjected to exposure (irradiation preferably withelectron beams (EB), X-rays or EUV rays) generally through a mask,preferably baking (heating), and then development. Thus, a good patterncan be obtained.

In a developing process, an alkali developer is used as follows. As thealkali developer for a resist composition, for example, alkaline aqueoussolutions such as inorganic alkalis, e.g., sodium hydroxide, potassiumhydroxide, sodium carbonate, sodium silicate, sodium metasilicate,aqueous ammonia, etc., primary amines, e.g., ethylamine, n-propylamine,etc., secondary amines, e.g., diethylamine, di-n-butylamine, etc.,tertiary amines, e.g., triethylamine, methyldiethylamine, etc., alcoholamines, e.g., dimethylethanolamine, triethanolamine, etc., quaternaryammonium salts, e.g., tetramethylammonium hydroxide, tetraethylammoniumhydroxide, etc., and cyclic amines, e.g., pyrrole, piperidine, etc., canbe used.

Further, appropriate amounts of alcohols and surfactants can be added tothe above alkali developers.

The alkali concentration of the alkali developer is generally 0.1 to 20%by mass.

The pH of the alkali developer is generally 10.0 to 15.0.

EXAMPLE

The invention will be described in further detail with reference toexamples but the invention is not restricted thereto.

Synthesis Example 1

Synthesis of Polymer (P-1)

(1) Synthesis of 4-styrenesulfonic acid triphenylsulfonium salt

Triphenylsulfonium Br salt (50 g) is dissolved in 65 ml of methanol. Amixed liquid of 30 g of 4-styrenesulfonic acid Na salt, 65 ml ofmethanol, and 130 ml of ion exchange water is dripped to the abovesolution at room temperature with stirring. To the solution are addedion exchange water and chloroform to perform extraction and washing.After an organic layer is concentrated, precipitated solid is slurriedin hexane/ethyl acetate and filtered to obtain 48 g of 4-styrenesulfonicacid triphenylsulfonium salt.

(2) Synthesis of Polymer (P-1)

1-Methoxy-2-propanol (10 ml) is heated at 80° C. in nitrogen current. Amixed solution comprising 3.0 g (25 mmol) of 4-hydroxystyrene, 1.2 g (10mmol) of 4-methylstyrene, 6.4 g (45 mmol) of t-butyl methacrylate, 1.1 g(2.5 mmol) of 4-styrenesulfonic acid triphenylsulfonium salt, 1.2 g (5.2mmol) of dimethyl 2,2′-azobisisobutyrate (V-601, manufactured by WakoPure Chemical Industries), and 20 ml of 1-methoxy-2-propanol is drippedto the above liquid while stirring over 5 hours. After termination ofdripping, the reaction solution is further stirred at 80° C. for 3hours. After cooling the reaction solution, the solution isreprecipitated with a large amount of hexane/ethyl acetate andvacuum-dried to obtain 7.0 g of resin (P-1) of the invention. Onmeasurement of ¹H-NMR of the obtained resin, a peak presumably resultingfrom the OH group of 4-hydroxystyrene in the vicinity of 9.0 ppm, a peakpresumably resulting from the methyl group of 4-methylstyrene in thevicinity of 2.3 ppm, a peak presumably resulting from the t-butyl groupof t-butyl methacrylate in the vicinity of 1.4 ppm, and a peakpresumably resulting from the phenyl group of the cationic part of4-styrenesulfonic acid triphenylsulfonium salt in the vicinity of 7.8ppm are respectively observed, thus the structure of resin (P-1) isconfirmed. From the area ratio of these peaks, the composition ratio(from the left side in order of the repeating unit in the structuralformula of resin (P-1) shown above, 35/15/45/5, in molar ratio) of theresin is computed. The weight average molecular weight (Mw: polystyreneequivalent) found from GPC (carrier: N-methyl-2-pyrrolidone (NMP)) isMw: 4,500, and Mw/Mn: 1.7.

Synthesis Example 2

Synthesis of Polymer (P-2)

(1) Synthesis of 3,4,4-trifluoro-4-sulfobutyl methacrylatetriphenylsulfonium salt

Triphenylsulfonium Br salt (50 g) is dissolved in 65 ml of methanol. Amixed liquid of 39 g of 1,1,2-trifluoro-4-hydroxy-1-butanesulfonatelithium salt (synthesized according to the method described in SolidState Ionics, 1999, 123, 233), 65 ml of methanol, and 130 ml of ionexchange water is dripped to the above solution at room temperature withstirring. To the solution are added ion exchange water and chloroform toperform extraction and washing. After an organic layer is concentrated,precipitated solid is slurried in hexane/ethyl acetate and filtered toobtain 31 g (40%) of 3,4,4-trifluoro-4-sulfobutyl methacrylatetriphenylsulfonium salt.

(2) Synthesis of Polymer (P-2)

1-Methoxy-2-propanol (10 ml) is heated at 80° C. in nitrogen current. Amixed solution comprising 3.0 g (25 mmol) of 4-hydroxystyrene, 1.3 g(9.7 mmol) of 4-methylstyrene, 6.4 g (45 mmol) of t-butyl methacrylate,1.3 g (2.4 mmol) of 3,4,4-trifluoro-4-sulfobutyl methacrylatetriphenylsulfonium salt, 1.2 g (5.2 mmol) of dimethyl2,2′-azobisisobutyrate (V-601, manufactured by Wako Pure ChemicalIndustries), and 20 ml of 1-methoxy-2-propanol is dripped to the aboveliquid while stirring over 5 hours. After termination of dripping, thereaction solution is further stirred at 80° C. for 3 hours. Aftercooling the reaction solution, the solution is reprecipitated with alarge amount of hexane/ethyl acetate and vacuum-dried to obtain 6.6 g ofresin (P-2) of the invention. On measurement of ¹H-NMR of the obtainedresin, a peak presumably resulting from the OH group of 4-hydroxystyrenein the vicinity of 9.0 ppm, a peak presumably resulting from the methoxygroup of 4-methoxystyrene in the vicinity of 3.7 ppm, a peak presumablyresulting from the t-butyl group of t-butyl methacrylate in the vicinityof 1.4 ppm, and a peak presumably resulting from the phenyl group of thecationic part of 3,4,4-trifluoro-4-sulfobutyl methacrylatetriphenylsulfonium salt in the vicinity of 7.8 ppm are respectivelyobserved, thus the structure of resin (P-2) is confirmed. From the arearatio of these peaks, the composition ratio (from the left side in orderof the repeating unit in the structural formula of resin (P-2) shownabove, 34/16/44/6, in molar ratio) of the resin is computed. The weightaverage molecular weight (Mw: polystyrene equivalent) found from GPC(carrier: N-methyl-2-pyrrolidone (NMP)) is Mw: 4,700, and Mw/Mn: 1.75.

Synthesis Example 3

Synthesis of Polymer (P-3)

1-Methoxy-2-propanol (17.5 ml) is heated at 80° C. in nitrogen current.A mixed solution comprising 10.3 g (85.4 mmol) of 4-hydroxystyrene, 8.0g (38.2 mmol) of 2-cyclohexyl-2-propyl methacrylate, 1.7 g (3.8 mmol) of4-styrenesulfonic acid triphenylsulfonium salt, 5.9 g (25.5 mmol) ofdimethyl 2,2′-azobisisobutyrate (V-601, manufactured by Wako PureChemical Industries), and 70 ml of 1-methoxy-2-propanol is dripped tothe above liquid while stirring over 4 hours. After termination ofdripping, the reaction solution is further stirred at 80° C. for 2hours. After cooling the reaction solution, the solution isreprecipitated with a large amount of hexane/ethyl acetate andvacuum-dried to obtain 17.1 g of polymer (P-3) of the invention. Onmeasurement of ¹H-NMR of the obtained polymer, a peak presumablyresulting from the OH group of 4-hydroxystyrene in the vicinity of 9.0ppm, and a peak presumably resulting from the phenyl group of thecationic part of 4-styrenesulfonic acid triphenylsulfonium salt in thevicinity of 7.8 ppm are respectively observed. Further, peaks presumablyresulting from the methylene group and methine group of 4-hydroxystyreneand 4-styrenesulfonic acid triphenylsulfonium salt in the vicinity of0.0 to 2.0 ppm are observed, and at the same time a peak presumablyresulting from 2-cyclohexyl-2-propyl methacrylate is observed, thus thestructure of polymer (P-3) is confirmed. From the area ratio of thesepeaks, the composition ratio (from the left side in order of therepeating unit in the structural formula of resin (P-3) shown above,60/37/3, in molar ratio) of the polymer is computed. The weight averagemolecular weight found from GPC is Mw: 5,000, and Mw/Mn: 1.6.

Other resins are also synthesized in the same manner.

Examples 1 to 35 and Comparative Examples 1 to 5

<Resist Evaluation (EB)>

The components shown in Table 1 below are dissolved in the mixed solventshown in Table 1 and a solution having solids content concentration of5.0% by mass is prepared. The solution is filtered through apolytetrafluoroethylene filter having a pore size of 0.1 μm, and apositive resist solution is obtained. The prepared positive resistsolution is uniformly coated with a spin coater on a silicon substratehaving been treated with hexamethyldisilazane, the substrate is dried ona hot plate by heating at 110° C. for 90 seconds, and a resist filmhaving a thickness of 100 nm is formed.

The resist film is irradiated with electron beam by an electron beamirradiating apparatus (HL750, accelerating voltage: 50 KeV, manufacturedby Hitachi Ltd.). Immediately after irradiation, the resist film isheated at 130° C. for 90 seconds on a hot plate. The resist film is thendeveloped with a tetramethylammonium hydroxide aqueous solution havingconcentration of 2.38% by mass at 23° C. for 60 seconds, rinsed withpure water for 30 seconds, and dried to form a line and space pattern.The obtained pattern is evaluated by the methods shown below.

[Sensitivity]

The form of the cross section of the obtained pattern is observed with ascanning electron microscope (S-9220, manufactured by Hitachi Limited).The minimum irradiation energy for resolving a 100 nm line (line andspace: 1/1) is taken as sensitivity.

[Resolution]

Limiting resolution in the irradiation quantity showing the abovesensitivity (the minimum line width capable of separation-resolving theline and space) is taken as resolution.

[Line Edge Roughness (LER)]

Concerning ordinary 30 points in the longitudinal direction 50 μm of 100nm line pattern in the irradiation quantity showing the abovesensitivity, the distance from the intrinsic base line of the edge ismeasured with a scanning electron microscope (S-9220, manufactured byHitachi, Ltd.), and standard deviation is found and 3σ is computed.

[Pattern Form]

The form of the cross section of the 100 nm line pattern in theirradiation quantity showing the above sensitivity is observed with ascanning electron microscope (S-4300, manufactured by Hitachi Limited),and three-stage evaluation of rectangle, a little taper and taper isperformed.

[Outgassing]

Evaluation is performed by the degree of variability (Z) of the filmthickness at the time of irradiation with the minimum irradiation energyfor resolving 100 nm line (line and space: 1/1).Z={[(film thickness before exposure)−(film thickness afterexposure)]/(film thickness before exposure)}×100(%)

Here, the film thickness after exposure indicates the film thicknessimmediately after exposure and is the film thickness before entering PEBand alkali developing process. The smaller the value, the better is theperformance.

TABLE 1 Results of evaluation by EB exposure Resin 1 Resin 2Conventional [Composition Ratio]*1 [Composition Ratio]*1 Acid-GeneratingEx. <Mw, Mw/Mn>*2 <Mw, Mw/Mn>*2 Agent Basic Cpd. Surfactant No.(Concentration)*3 (Concentration)*3 (concentration)*3 (concentration)*3(concentration)*3 Ex. 1 P-1  None None None W-1 [35/15/45/5] (0.05)<4,500, 1.7>  (99.95) Ex. 2 P-1  None None None W-1 [35/15/45/5] (0.05)<4,500, 1.7>  (99.95) Ex. 3 P-2  None None None W-1 [34/16/44/6] (0.05)<4,700, 1.75> (99.95) Ex. 4 P-3  None None None W-2 [60/37/3] (0.05)<5,000, 1.6>  (99.95) Ex. 5 P-4  None None None W-3 [36/14/45/5] (0.05)<5,000, 1.75> (99.95) Ex. 6 P-12 None None None W-1 [36/14/46/4] (0.05)<4,700, 1.73> (99.95) Ex. 7 P-19 None None None W-1 [35/15/47/3] (0.05)<4,800, 1.86> (99.95) Ex. 8 P-21 None None None W-1 [47.5/46.5/6] (0.05)<4,500, 1.90> (99.95) Ex. 9 P-21 None None None W-1 [47.5/46.5/6] (0.05)<4,700, 1.66> (99.95) Ex. 10 P-21 None None None W-1 [47.5/46.5/6](0.05) <4,500, 1.90> (99.95) Ex. 11 P-29 None None None W-1 [48/47/5](0.05) <4,500, 1.80> (99.95) Ex. 12 P-30 None None None W-1 [50/45/5](0.05) <4,500, 1.80> (99.95) Ex. 13 P-35 None None None W-1 [30/18/47/5](0.05) <4,700, 1.66> (99.95) Ex. 14 P-44 None None None W-1 [35/15/45/5](0.05) <4,500, 1.91> (99.95) Ex. 15 P-48 None None None W-2 [37/13/45/5](0.05) <4,300, 1.65> (99.95) Ex. 16 P-59 None None None W-3 [35/15/46/4](0.05) <4,300, 1.65> (99.95) Ex. 17 P-4  P-44 None None W-1 [50/0/44/6][0/50/45/5] (0.05) <5,000, 1.75>  <4,300, 1.65> (74.95) (25) Ex. 18 P-4 P-48 None None W-1 [52/0/42/6] [0/50/45/5] (0.05) <5,000, 1.75>  <4,300,1.65> (74.95) (25) Ex. 19 P-2  PR-1   None None W-1 [29/26/40/5] [70/30](0.05) <4,500, 1.65> <19,000, 1.14> (84.95) (15) Ex. 20 P-2  None NoneTPI W-1 [34/16/44/6] (0.3) (0.05) <4,500, 1.65> (99.65) Ex. 21 P-2  NonePAG-1 TPI W-1 [34/16/44/6] (1) (0.3) (0.05) <4,500, 1.65> (98.65) Ex. 22P-4  PR-2 None None W-1 [36/14/45/5] [70/30] (0.05) <5,000, 1.75><20,000, 1.15> (66.95) (33) Ex. 23 P-4  None PAG-1 TBAH W-1 [36/14/45/5](2) (0.5) (0.05) <5,000, 1.75> (97.45) Ex. 24 P-44 None PAG-1 TBAH W-1[35.5/14.5/44/6] (2) (0.5) (0.05) <4,500, 1.91> (97.45) Ex. 25 P-22 NoneNone TBAH W-1 [45/12/37/6] (0.3) (0.05) <4,600, 1.85> (99.65) Ex. 26P-29 None None TBAH W-1 [50/46/4] (0.3) (0.05) <5,100, 1.89> (99.65) Ex.27 P-40 None None TBAH W-1 [46/11/37/6] (0.3) (0.05) <4,750, 1.81>(99.65) Ex. 28 P-55 None None TBAH W-1 [45/10/37/8] (0.3) (0.05) <6,200,1.85> (99.65) Ex. 29 P-61 None None TBAH W-1 [51/10/33/6] (0.3) (0.05)<4,500, 1.91> (99.65) Ex. 30 P-62 None None TBAH W-1 [52/10/32/6] (0.3)(0.05) <5,000, 1.86> (99.65) Ex. 31 P-66 None None TBAH W-1 [55/10/29/6](0.3) (0.05) <4,850, 1.83> (99.65) Ex. 32 P-72 None None TBAH W-1 [40/20/30/10] (0.3) (0.05) <5,250, 1.79> (99.65) Ex. 33 P-75 None NoneTBAH W-1 [61/36/3] (0.3) (0.05) <5,250, 1.79> (99.65) Ex. 34 P-1  NoneNone None None [35/15/45/5] <4,500, 1.7>  (100)    Ex. 35 P-1  None NoneNone W-1 [35/15/45/5] (0.05) <4,500, 1.7>  (100)    Comp. PR-1   NonePAG-1 None W-1 Ex. 1 [70/30] (8) (0.05) <19,000, 1.14>  (91.95) Comp.PR-1   None PAG-1 TPI W-1 Ex. 2 [70/30] (8) (1.5) (0.05) <19,000, 1.14> (90.45) Comp. PR-1   PR-3 None None W-1 Ex. 3 [70/30] [70/30] (0.05)<19,000, 1.14>  <21,000, 1.85> (50)     (49.95) Comp. PR-4   None NoneNone W-1 Ex. 4 [17/50/30/3] (0.05) <38,500, 2.55>  (99.95) Comp. P-1 None None None W-1 Ex. 5 [35/15/45/5] (0.05) <4,500, 1.7>  (99.95)Organic Solvent Ex. (mixing Sensitivity Resolution Pattern LEROutgassing No. ratio)*4 (μC/cm²) (nm) Form (nm) (Z) Remarks Ex. 1 S1/S223 65 Rectangle 5.0 5.1 — (40/60) Ex. 2 S1/S6 23.1 65 Rectangle 4.9 5.9— (80/20) Ex. 3 S1/S5 21 60 Rectangle 4.7 4.9 — (40/60) Ex. 4 S1/S2 18.565 Rectangle 4.0 3.7 — (40/60) Ex. 5 S1/S2 17.1 65 Rectangle 4.9 3.7 —(40/60) Ex. 6 S1/S2 17 65 Rectangle 4.9 3.5 — (40/60) Ex. 7 S1/S2 23.555 Rectangle 4.5 3 — (40/60) Ex. 8 S1/S2 18.5 60 Rectangle 4.3 3.2 —(40/60) Ex. 9 S1/S2 19.5 55 Rectangle 4.0 4.5 — (60/40) Ex. 10 S1/S216.9 65 Rectangle 4.8 4.1 — (40/60) Ex. 11 S1/S2 16.8 65 Rectangle 5.04.5 — (40/60) Ex. 12 S1/S2 17 65 Rectangle 4.9 4.1 — (40/60) Ex. 13S1/S2 22.4 65 Rectangle 4.5 4.5 — (40/60) Ex. 14 S1/S2 18.5 60 Rectangle5.0 3.5 — (40/60) Ex. 15 S1/S2 17.5 60 Rectangle 4.5 3.4 — (40/60) Ex.16 S2/S3 25 65 Rectangle 5.5 5.5 — (60/40) Ex. 17 S1/S2 18 60 Rectangle5.0 3.6 — (40/60) Ex. 18 S1/S2 17.3 60 Rectangle 4.8 3.7 — (40/60) Ex.19 S2/S4 23.8 65 Rectangle 5.5 8 — (60/40) Ex. 20 S1/S2 33.1 60Rectangle 4.3 5 — (40/60) Ex. 21 S1/S2 28 65 Rectangle 5.1 5.1 — (40/60)Ex. 22 S1/S2 18 65 Rectangle 5.2 4.1 — (40/60) Ex. 23 S1/S2 19.7 60Rectangle 4.3 4 — (50/50) Ex. 24 S1/S2 26.5 60 Rectangle 7.5 4 — (50/50)Ex. 25 S1/S2 22 60 Rectangle 4.4 5.2 — (50/50) Ex. 26 S1/S2 22 65Rectangle 4.6 5.5 — (50/50) Ex. 27 S1/S2 23 60 Rectangle 4.5 5.2 —(50/50) Ex. 28 S1/S2 25 65 Rectangle 4.4 5.1 — (50/50) Ex. 29 S1/S2 2160 Rectangle 4.5 5 — (50/50) Ex. 30 S1/S2 20 60 Rectangle 4.3 5.1 —(50/50) Ex. 31 S1/S2 19 60 Rectangle 4.1 5.1 — (50/50) Ex. 32 S1/S6 2060 Rectangle 4.2 4.8 — (70/30) Ex. 33 S1/S2 23 55 Rectangle 4.0 5.4 —(40/60) Ex. 34 S1/S6 22.5 65 Rectangle 5.0 6.5 — (70/30) Ex. 35 S1/S622.1 65 Rectangle 5.2 7.6 — (60/40) Comp. S1/S2 — — — — 10.6 100 nm Ex.1 (40/60) L/S pattern cannot be formed Comp. S1/S2 22.8 90 Taper 12.610.5 — Ex. 2 (40/60) Comp. S1/S2 27.6 85 Taper 10.2 9.1 — Ex. 3 (40/60)Comp. S1/S2 — — — — 8.5 100 nm Ex. 4 (40/60) L/S pattern cannot beformed Comp. S6 23.1 65 Rectangle 5.1 8.3 — Ex. 5 *1: Molar ratio *2: Mwand Mn are respectively weight average molecular weight and numberaverage molecular weight as polystyrene equivalent found by GPC(carrier: N-methyl-2-pyrrolidone (NMP)) *3: % by mass in all the solidscontent *4: Mass ratio

In Comparative Examples 1 and 4, patterns of 100 nm line (line andspace: 1/1) cannot be formed.

From Table 1, it is apparent that the actinic ray-sensitive orradiation-sensitive resin compositions in the invention can satisfy highsensitivity, high resolution, good pattern form, good line edgeroughness and reduction of outgassing at the same time.

The structures of the materials (other resins, conventional acidgenerators and basic compounds) used in examples and comparativeexamples are shown below.

The surfactants and solvents used in examples and comparative examplesare shown below.

-   W-1: Megafac F 176 (fluorine surfactant, manufactured by Dainippon    Ink and Chemicals Inc.)-   W-2: Megafac R08 (fluorine/silicon surfactant, manufactured by    Dainippon Ink and Chemicals Inc.)-   W-3: Polysiloxane polymer (silicon surfactant, manufactured by    Shin-Etsu Chemical Co., Ltd.)-   S1: Propylene glycol monomethyl ether acetate (PGMEA, b.p.: 146° C.)-   S2: Propylene glycol monomethyl ether (PGME, b.p.: 120° C.)-   S3: Methyl lactate (b.p.: 145° C.)-   S4: 5-Methyl-2-hexanone (b.p.: 145° C.)-   S5: Propylene glycol monoethyl ether (b.p.: 130-131° C.)-   S6: Cyclohexanone (b.p.: 157° C.)

Examples 36 to 38

<Resist Evaluation (EUV)>

The components shown in Table 2 below are dissolved in the mixed solventshown in Table 2 and a solution having solids content concentration of5.0% by mass is prepared. The solution is filtered through apolytetrafluoroethylene filter having a pore size of 0.1 μm, and apositive resist solution is obtained. The symbols in Table 2 are thesame as those in Table 1.

The prepared positive resist solution is uniformly coated with a spincoater on a silicon substrate having been treated withhexamethyldisilazane, the substrate is dried on a hot plate by heatingat 120° C. for 90 seconds, and a resist film having a thickness of 100nm is formed.

The resist film is irradiated with EUV exposure apparatus (wavelength:13 nm). Immediately after irradiation, the resist film is heated at 130°C. for 90 seconds on a hot plate. The resist film is then developed witha tetramethylammonium hydroxide aqueous solution having concentration of2.38% by mass at 23° C. for 60 seconds, rinsed with pure water for 30seconds, and dried to form a line and space pattern (line and space:1/1). The obtained pattern is evaluated by the methods shown below.

[Sensitivity]

The form of the cross section of the obtained pattern is observed with ascanning electron microscope (S-9220, manufactured by Hitachi Limited).The minimum irradiation energy for resolving a 100 nm line (line andspace: 1/1) is taken as sensitivity.

[Pattern Form]

The form of the cross section of the 100 nm line pattern in theirradiation quantity showing the above sensitivity is observed with ascanning electron microscope (S-4300, manufactured by Hitachi Limited),and three-stage evaluation of rectangle, a little taper and taper isperformed.

TABLE 2 Results of evaluation by EUV exposure Resin 1 Resin 2Conventional Organic [Composition Ratio]*1 [Composition Ratio]*1Acid-Generating Basic Solvent Ex. <Mw, Mw/Mn>*2 <Mw, Mw/Mn>*2 AgentCompound Surfactant (mixing Sensitivity Pattern No. (concentration)*3(concentration)*3 (concentration)*3 (concentration)*3 (concentration)*3ratio)*4 (μC/cm²) Form Ex. P-4  None None None W-3 S1/S2 25.7 Rectangle36 [36/14/44/6] (0.05) (40/60) <5,000, 1.75> (99.95) Ex. P-11 None NoneNone W-1 S1/S2 26.8 Rectangle 37 [35/15/45/5] (0.05) (40/60) <4,700,1.67> (99.95) Ex. P-30 None None None W-1 S1/S2 25.1 Rectangle 38[50/45/5] (0.05) (40/60) <4,500, 1.80> (99.95) *1: Molar ratio *2: Mwand Mn are respectively weight average molecular weight and numberaverage molecular weight as polystyrene equivalent found by GPC(carrier: N-methyl-2-pyrrolidone (NMP)) *3: % by mass in all the solidscontent *4: Mass ratio

From the results shown in Table 2, the actinic ray-sensitive orradiation-sensitive resin compositions in the invention can also showgood sensitivity and form a good pattern form even with EUV exposure.

According to the invention, an actinic ray-sensitive orradiation-sensitive resin composition satisfying high sensitivity, highresolution, good pattern form, good line edge roughness and reduction ofoutgassing at the same time in a super fine region, in particular, inelectron beam, X-ray or EUV ray lithography, and suitable as a positiveresist composition, and a pattern-forming method using the compositioncan be provided.

The entire disclosure of Japanese Patent Application Nos. 2009-083708and 2010-013681 filed on Mar. 30, 2009 and Jan. 25, 2010 respectively,from which the benefit of foreign priority has been claimed in thepresent application, is incorporated herein by reference, as if fullyset forth.

1. An actinic ray-sensitive or radiation-sensitive resin compositioncomprising: (P) a resin that contains the following repeating units (A),(B) and (C); and a solvent having a boiling temperature of 150° C. orless, (A) a repeating unit containing a group capable of decomposing andforming an acid upon irradiation with an actinic ray or radiation, (B) arepeating unit containing a group capable of decomposing and forming acarboxylic acid by the action of an acid, and (C) a repeating unitcontaining a carbon-carbon unsaturated bond, wherein (A) is a repeatingunit represented by formula (III), formula (IV) or formula (V):

wherein each of R₀₄, R₀₅ and R₀₇ to R₀₉ independently represents ahydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, acyano group, or an alkoxycarbonyl group; R₀₆ represents a hydrogen atom,a cyano group, a carboxyl group, —CO—OR₂₅, or —CO—N(R₂₆)(R₂₇), R₂₆ andR₂₇ may be bonded to form a ring with a nitrogen atom; each of X₁, X₂,and X₃ independently represents a single bond, an arylene group analkylene group, a cycloalkylene group, —O—, —SO₂—, —CO—, —N(R₃₃)—, or adivalent linking group obtained by combining two or more of thesegroups, provided that X₁ to X₃ contain an arylene group; R₂₅ representsan alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, oran aralkyl group; each of R₂₆, R₂₇ and R₃₃ independently represents ahydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, anaryl group, or an aralkyl group; A represents a structural part capableof decomposing and generating an acid upon irradiation with an actinicray or radiation.
 2. The actinic ray-sensitive or radiation-sensitiveresin composition as claimed in claim 1, wherein the repeating unit (B)is a repeating unit represented by the following formula (I), and therepeating unit (C) is a repeating unit represented by the followingformula (II):

wherein each of R₀₁, R₀₂ and R₀₃ independently represents a hydrogenatom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group,or an alkoxycarbonyl group, and R₀₃ may represent an alkylene group andbe bonded to L or Q to form a 5- or 6-membered ring; L represents asingle bond or a divalent linking group, provided that L represents atrivalent linking group when bonded to R₀₃ to form a 5- or 6-memberedring; R₁ represents an alkyl group; each of R₂ and R₃ independentlyrepresents a hydrogen atom, an alkyl group, a cycloalkyl group or anaryl group, and R₂ and R₃ may be bonded to each other to form a ring,provided that R₂ and R₃ do not represent a hydrogen atom at the sametime; and Q represents a group containing a carbon-carbon unsaturatedbond.
 3. The actinic ray-sensitive or radiation-sensitive resincomposition as claimed in claim 2, wherein Q in formula (II) is a groupcontaining an aromatic ring.
 4. The actinic ray-sensitive orradiation-sensitive resin composition as claimed in claim 3, wherein Qin formula (II) is a group containing a benzene ring.
 5. The actinicray-sensitive or radiation-sensitive resin composition as claimed inclaim 1, wherein the compositional amount (mol) of the repeating unit(B) and the repeating unit (C) in the resin (P) satisfies a relationshipof the repeating unit (B)≦the repeating unit (C).
 6. The actinicray-sensitive or radiation-sensitive resin composition as claimed inclaim 1, wherein the resin (P) further contains (D) a repeating unitwhich has a group capable of decomposing by the action of an alkalideveloper and increasing a dissolution rate in the alkali developer andwhich is represented by the following formula (AII):

wherein Rb₀ represents a hydrogen atom, a halogen atom or an alkylgroup; Ab represents a single bond, an alkylene group, a divalentlinking group having a monocyclic or polycyclic alicyclic hydrocarbonstructure, an ether bond, an ester bond, a carbonyl group, or a divalentlinking group combining these; and V represents a group capable ofdecomposing by the action of an alkali developer and increasing adissolution rate in the alkali developer.
 7. The actinic ray-sensitiveor radiation-sensitive resin composition as claimed in claim 1, whereinthe resin (P) contains, as the repeating unit (C), a repeating unitderived from hydroxystyrene or a derivative thereof.
 8. The actinicray-sensitive or radiation-sensitive resin composition as claimed inclaim 1, wherein the repeating unit (A) has a structure capable ofgenerating an acid anion on the side chain of the resin upon irradiationwith an actinic ray or radiation.
 9. The actinic ray-sensitive orradiation-sensitive resin composition as claimed in claim 1, wherein thesolvent having a boiling temperature of 150° C. or less is contained inan amount of 75% by mass or more based on all the amount of solvents.10. The actinic ray-sensitive or radiation-sensitive resin compositionas claimed in claim 1, wherein the resin (P) consists of the repeatingunits (A) to (C) alone, and all of the repeating unit (C) are arepeating unit represented by the following formula (II-1):

wherein Q represents a group containing a carbon-carbon unsaturatedbond.
 11. The actinic ray-sensitive or radiation-sensitive resincomposition as claimed in claim 1 wherein the resin (P) consists of therepeating units (A) to (D) alone, and all of the repeating unit (C) area repeating unit represented by the following formula (II-1):

wherein Q represents a group-containing a carbon-carbon unsaturatedbond.
 12. The actinic ray-sensitive or radiation-sensitive resincomposition as claimed in claim 1, wherein the proportion of a repeatingunit having a cyclic structure in the main chain in the resin (P) is 30mol % or less.
 13. The actinic ray-sensitive or radiation-sensitiveresin composition as claimed in claim 1, wherein the resin (P) does notcontain a repeating unit having a cyclic structure in the main chain.14. The actinic ray-sensitive or radiation-sensitive resin compositionas claimed in claim 1, wherein the resin (P) has a weight averagemolecular weight in the range of 1,000 to 100,000.
 15. The actinicray-sensitive or radiation-sensitive resin composition as claimed inclaim 1, further comprising: a basic compound.
 16. A resist film formedwith the actinic ray-sensitive or radiation-sensitive resin compositionclaimed in claim
 1. 17. A pattern-forming method comprising: exposingand developing the resist film claimed in claim
 16. 18. Thepattern-forming method according to claim 17, wherein the exposing isperformed with an electron beam, an X-ray or an EUV ray.
 19. The actinicray-sensitive or radiation-sensitive resin composition according toclaim 1, provided that X₁ to X₃ contain an arylene group and —SO₂—. 20.An actinic ray-sensitive or radiation-sensitive resin compositioncomprising: (P) a resin that contains the following repeating units (A),(B) and (C); and a solvent having a boiling temperature of 150° C. orless, (A) a repeating unit containing a group capable of decomposing andforming an acid upon irradiation with an actinic ray or radiation, (B) arepeating unit containing a group capable of decomposing and forming acarboxylic acid by the action of an acid, and (C) a repeating unitcontaining a carbon-carbon unsaturated bond, wherein the solvent havinga boiling temperature of 150° C. or less is contained in an amount of75% by mass or more based on all the amount of solvents.
 21. The actinicray-sensitive or radiation-sensitive resin composition as claimed inclaim 20 wherein the solvent having a boiling temperature of 150° C. orless is contained in an amount of 90% by mass or more based on all theamount of solvents.